Certain alkyloxalyl amino substituted s-triazines herbicides

ABSTRACT

Compounds having the formula   WHEREIN R is chlorine, methylthio or ethylthio, R1, R2, and R3 are alkyl, and their uses as herbicides.

United States Patent MacDonald 5] Dec. 9, 1975 1 CERTAIN ALKYLOXALYL AMINO 3,790,570 2/1974 Perronnet et a1. 71/93 x SUBSTITUTED SJIRIAZINES HERBICIDES 3,817,741 6/1974 Kuhne et a1. 71/93 [75] Inventor: Alan A. MacDonald, Albany, Calif.

[73] Assignee: Stauffer Chemical Company,

Westport, Conn.

[22] Filed: Aug. 23, 1974 [21] Appl. No.: 500,202

Related U.S. Application Data [62] Division of Ser, No. 347,296, April 2, 1973, Pat. No

[52] U.S. Cl. 71/93; 71/76; 71/74 [51] Int. Cl. AOlN 9/22 [58] Field of Search 71/93 [56] References Cited UNITED STATES PATENTS 3,236,846 2/1966 Kunsli el al 71/93 X 3,773,763 11/1973 Wells et al. i i i i M 71/93 X 3,786,053 l/1974 Chapman et al 71/93 X Primary Examiner-Lewis Gotts Assistant ExaminerCatherine L. Mills Attorney, Agent, or Firm-Edwin H, Baker 1 1 ABSTRACT Compounds having the formula wherein R is chlorine, methylthio or ethylthio, R, R and R are alkyl, and their uses as herbicides.

6 Claims, N0 Drawings CERTAIN ALKYLOXALYL AMINO SUBSTITUTED S-TRIAZINES HERBICIDES This is a division, of application Ser. No. 347,296 filed Apr. 2, 1973 US. Pat. No. 3,856,793.

This invention relates to certain novel alkyloxalylamino substituted s-triazines which are useful as herbicides.

The compounds of the present invention have the formula where R is chlorine, methylthio or ethylthio, preferably chlorine or methylthio; R is alkyl having 1 to 4 carbon atoms, preferably having 1 to 2 carbon atoms; R is alkyl having 1 to 4 carbon atoms, preferably having l to 2 carbon atoms, and R is alkyl having 1 to 4 carbon atoms, preferably having 1 to 3 carbon atoms.

The alkyl groups are either straight, branched or cyclic.

The compounds of this invention are active herbi cides of a general type. That is, they are herbicidally effective against a wide range of plant species. The method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds to the area where control is desired.

An herbicide is used herein to mean a compound which controls or modifies the growth of plants. By a growth controlling amount" is meant an amount of compound which causes a modifying effect upon the growth of plants. Such modifying effects include all deviations from natural development, for example, killing, retardation, defoliation, dessiccation, regulation, stunting, tillering, stimulating, dwarfing and the like. By "plants", it is meant germinating seeds, emerging seedlings, and established vegetation including the roots and above-ground portions.

The compounds of the present invention can be prepared by the following reaction:

EXAMPLE 2-chloro-4-(ethyl oxalyl) ethylamino'6-isopropylamino-striazine 2 5 O N hlll h s A 10.8 grams (0.05 mols) of 2-chloro-4-ethylamino-6- isopropylamino-s-triazine and 6.9 grams (0.05 mole) o1 ethyl oxalyl chloride are combined with 100 ml. 1,2- dichloroethane in a 500 ml. 3-neck flask equipped witl a stirrer, thermometer and reflux condenser. The mix ture is reflux for 9 hours. It is then cooled to room tem perature and filtered. Evaporation of the solvent leave: the desired product, a viscous light amber liquid. The structure is confirmed by n.m.r.

The following is a table of certain selected com pounds that are preparable according to the procedure described hereto. Compound numbers are assigned tr each compound and are used through the remainder o' the application.

TABLE I o N)\N o O R l \"JkT/k JN II COMPOUND N or NUMBER R R R R m.p.

1. chlorine methyl ethyl i-propyl 1.4960 2. methylthio ethyl ethyl i-propyl 1.5153 3. methylthio ethyl i-propyl i-propyl l .S 160 4. chlorine methyl ethyl ethyl 5. methylthio methyl ethyl ethyl 6. methylthio ethyl ethyl ethyl 7. chlorine methyl ethyl i-propyl 1.5097 8. methylthio methyl ethyl i-propy1 9. methylthio methyl ethyl t-butyl 1.5 280 ll). methylthio ethyl ethyl t-butyl 1.5 l9? 1 l. chlorine methyl i-propyl i-propyl 4 5 l2. chlorine ethyl i-propyl i-propyl l3. methylthio methyl i-propyl i propyl 14. chlorine ethyl ethyl ethyl l lBl22t l 5. chlorine ethyl ethyl i-propyl Prepared in the Example.

R NEDTLNHRS 5,2

Herbicidal Screening Tests As previously mentioned, the herein described con pounds produced in the above-described manner a1 phytotoxic compounds which are useful and valuable l controlling various plant species. Selected compoum of this invention are tested as herbicides in the follow ,5 ing manner.

Pre-emergence herbicide test.

On the day preceding treatment, seeds of seven d 3 ferent weed species are planted in individual rows using one species per row across the width of the flat. The seeds used are hairy crabgrass (Digitaris sanguinalis (L) Scop. yellow foxtail (Seraria glauca (L.) Beauv. watergrass (Echinochloa crusgalli (L.) Beauv. California red oat (Avena sativa (L), redroot pigweed (Amaranlhus retroflexus (L.), Indian mustard (Brassica juncea (L.) Coss.) and curly dock (Rumex crispus (L.). Ample seeds are planted to give about 20 to 50 seedlings per row, after emergence, depending upon the size of the plants. The flats are watered after planting. The spraying solution is prepared by dissolving 50 mg. of the test compound in 3 ml. of solvent, such as acetone, containing 1% Tween 20 (polyoxyethylene sorbitan monolau most fully expanded and the first trifoliate leaves are just starting to form, the plants are sprayed. The spray is prepared by weighing out 50 mg. of the test compound, dissolving it in 5 ml. of acetone containing 1% Tween (polyoxyethylene sorbitan monolaurate) and then adding 5 ml. of water. The solution is sprayed on the foliage using an atomizer. The spray concentration is 0.5% and the rate would be approximately 20 pounds per acre if all of the spray was retained on the plant and the soil, but some spray is lost so it is estimated that the rate). The following day each flat is sprayed at the rate application rate is approximately 12.5 pounds per of 20 pounds of the candidate compound per 80 gallons acre. zl h jl g BF? used to f Beans are used to detect defoliants and plant growth so u 2 onto t 5 a f l regulators. The beans are trimmed to two or three lgreen houge at f .and W2! erel r dg )f- :8 wee s 20 plants per flat by cutting off the excess weaker plants t agree 0 9? g i several days before treatment. The treated plants are 3 f f g f g i an g o placed back in the greenhouse and care is taken to wee m d 8 fl ats t e fi S 2 Severe avoid sprinkling the treated foliage with water for three a ,F Q h i g 0 t F tes are days after treatment. Water is applied to the soil by pone a 8 t e 0 owmg mung system means of a slow stream from a watering hose taking Post-emergence herbicide test. Care not to wet the foliage.

Seeds of five weed species previously recited,includ- Injury rates are recorded 14 days after treatment.

Rated as percent injury 0 no injury I00 complete control TABLE 11 PRE-EMERGENCE ACTIVITY RATE 20 LBS-IA Compound Crab Water Wild Curled Number grass Foxtail grass oat Pigweed Mustard dock 1. 95 90 70 so 70 I00 70 2. 95 70 so 30 I00 95 3. 90 8O 70 98 I00 90 4. 100 97 95 100 100 100 100 5. 98 I00 93 99 100 100 200 6. 100 95 95 so 100 90 100 7. 95 98 98 I00 100 100 100 8. 9s 9s 95 100 100 100 100 9. 98 95 95 30 I00 100 I00 10. 99 99 I00 20 100 100 [00 ll. 70 so 80 99 100 80 12. so 70 80 100 100 I00 13. 100 99 90 100 I00 14. 98 I00 80 100 100 100 80 i5. 100 I00 I00 I00 I00 100 98 ing hairy crabgrass, watergrass, California red oats, Indian mustard, and curly dock and one crop, pinto beans (Phaseolus vulgaris), are planted in flats as de- The rating system is the same as described above for the preemergence test where O no injury and I00 complete control. The results are reported in Table "I.

TABLE III POST-EMERGENCE ACTIVITY RATE 20 LBS/A.

COMPOUND CRAB WATER RED CURLED PINTO NUMBER GRASS GRASS OATS MUSTARD DOCK BEANS 1. I00 90 I00 I00 I00 I00 2. I00 95 I00 I00 95 I00 3. I00 95 I00 I00 95 I00 4. I00 I00 I00 I00 I00 I00 5. I00 98 I00 I00 I00 I00 6. I00 97 100 I00 80 I00 7. I00 I00 I00 I00 I00 I00 8. I00 98 I00 I00 98 I00 9. I00 98 I00 I00 I00 I00 [0. I00 I00 I00 I00 90 100 ll. 80 97 I00 I00 I00 I00 I2. I00 I00 I00 I00 99 100 I3. I00 99 I00 I00 95 100 I4. I00 I00 I00 I00 I00 I00 TABLE [ll-continued POST-EMERGENCE ACTlVlTY RATE 20 LBs/A. COMPOUND CRAB WATER RED CURLED PINTO NUMBER GRASS GRASS OATS MUSTARD DOCK BEANS I5. 100 100 100 100 I too The compounds of the present invention are used as pre-emergence or post-emergence herbicides and are applied in a variety of ways at various concentrations. In practice, the compounds herein defined are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds may be formulated as granules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. Preferred formulations for both preand post-emergence herbicidal applications are Wettable powders, emulsifiable concentrates and granules. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient. The amount applied depends upon the nature of the seeds or plants to be controlled and the rate of application varies from I to approximately 50 pounds per acre.

Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersant. The wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for Wettable powders include fullers earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. Wettable powders normally are prepared to contain about to about 95% of the active ingredient by weight and usually also contain a small amount of wetting, dispersing or emulsifying agent to facilitate wetting and dispersron.

Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises about 0.5 to 95% of active ingredient by weight of the herbicidal composition.

Granular formulations, wherein the toxicant is carried on relatively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fullers earth, bentonite clays, vermiculite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant. Granular formulations normally are prepared to contain about 5 to about of active ingredient and may also contain small amounts of other ingredients which may include surface-active agents such as wetting agents, dispersing agents or emulsifiers; oils such as heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.

Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; polyhydric alcohols; and other types of Surface-active agents, many of which are available in commerce. The surface-active agent, when used, normally comprises from 0.1 to 15% by weight of the herbicidal composition.

Dusts, which are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating applications.

Pastes, which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5 to about oi active ingredient by weight, and may also contain small amounts of a wetting, dispersing or emulsifying agent tc facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the area tc be affected.

Other useful formulations for herbicidal applications include simple solutions of the active ingredient in z dispersant in which it is completely soluble at the desired concentration, such as acetone, alkylated naph thalenes, xylene or other organic solvents. Pressurizet sprays, typically aerosols, wherein the active ingredien is dispersed in finely-divided form as a result of vapori zation of a low boiling dispersant solvent carrier, sucl as the Freons, may also be used.

The phytotoxic compositions of this invention are ap plied to the plants in the conventional manner. Thus the dusts and liquid compositions can be applied to th: plant by the use of power-dusters, boom and ham Sprayers and spray dusters. The compositions can alsi be applied from airplanes as a dust or a spray becausl they are effective in very low dosages. In order to mod ify or control growth of germinating seeds or emergin; seedlings, as a typical example, the dust and liquic compositions are applied to the soil according to con vention methods and are distributed in the soil to depth of at least h inch below the soil surface. It is no necessary that the phytotoxic compositions be admixe' with the soil particles since these compositions can als be applied merely by spraying or sprinkling the surfac of the soil. The phytotoxic compositions of this inven tion can also be applied by addition to irrigation wate supplied to the field to be treated. This method of a1: plication permits the penetration of the composition into the soil as the water is absorbed therein. Dust corr positions, granular compositions or liquid formulation applied to the surface of the soil can be distribute below the surface of the soil by conventional means such as discing, dragging or mixing operations.

The phytotoxic compositions of this invention can also contain other additaments, for example, fertilizers, pesticides and the like, used as adjuvant or in combination with any of the above-described adjuvants. Other phytotoxic compounds useful in combination with the above-described compounds include, for example, 2,4 dichlorophenoxyacetic acids, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid and the salts, esters and amides thereof; triazine derivatives, such as 2,4-bis(3-methoxypropylamino)-6-methylthios-triazine, 2-chloro-4-ethylamino-6-isopropylamino-striazine, and 2-ethylamino-4-isopropylamino-6methylmercapto-s-triazine; urea derivatives, such as 3-(3,4- dichlorophenyl)-l,l-dimethyl urea and 3-(p-ch1orophenyl)-l,l-dimethyl urea; and acetamides such as N,N-diallyla-chloroacetamide, and the like; benzoic acids such as 3-amino-2,5-dichlorobenzoic; thiocarbamates, such as S-propyl dipropylthiocarbamate, S- ethyldipropylthiocarbamate, S-ethyl cyclohexylethyl thiocarbamate, S-ethyl hexahydro-lH-azepine-l-carbothioate and the like; 4-(methylsulfonyl)-2,6-dinitro- N,N-substituted anilines, such as 4-(methylsulfonyl)- 2,6-dinitro-N,N-di-n-propyl aniline, 4-trifluoromethyl- 2,fi-dinitro-N,Nsubstituted anilines, such as 4-trifluoromethyl-Z,-dinitro-N,N-di-n-propyl anilines and 4-trifluoromethyl-2,6-dinitro-N-ethyl-N-n-butyl aniline.

Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. Other useful additaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand and the like.

The concentration of a compound of the present invention, constituting an effective amount in the best mode of administration in the utility disclosed is readily determinable by those skilled in the art.

it is claimed:

1. The method of controlling undesirable vegetation which comprises applying thereto an herbicidal amount of a compound having the formula where R is chlorine, methylthio or ethylthio; R is alkyl having I to 4 carbon atoms; R is alkyl having 1 to 4 carbon atoms; and R is alkyl having 1 to 4 carbon atoms.

2. The method of claim 1 in which R is chlorine, R is ethyl, R is ethyl and R is isopropyl.

3. The method of claim 1 in which R is chlorine, R is ethyl, R is ethyl and R is ethyl.

4. The method of claim 1 in which R is methylthio, R is ethyl, R is ethyl and R is ethyl.

5. The method of claim 1 in which R is chlorine, R is methyl, R is ethyl and R is isopropyl.

6. The method of claim 1 in which R is chlorine, R is methyl, R is ethyl and R is ethyl. 

1. THE METHOD OF CONTROLLING UNDESIRABLE VEGETATION WHICH COMPRISES APPLYING THERETO AN HERBICIDAL AMOUNT OF A COMPOUND HAVING THE FORMULA
 2. The method of claim 1 in which R is chlorine, R1 is ethyl, R2 is ethyl and R3 is isopropyl.
 3. The method of claim 1 in which R is chlorine, R1 is ethyl, R2 is ethyl and R3 is ethyl.
 4. The method of claim 1 in which R is methylthio, R1 is ethyl, R2 is ethyl and R3 is ethyl.
 5. The method of claim 1 in which R is chlorine, R1 is methyl, R2 is ethyl and R3 is isopropyl.
 6. The method of claim 1 in which R is chlorine, R1 is methyl, R2 is ethyl and R3 is ethyl. 